EP0400330B1 - Oxidation hair dyes - Google Patents
Oxidation hair dyes Download PDFInfo
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- EP0400330B1 EP0400330B1 EP90108017A EP90108017A EP0400330B1 EP 0400330 B1 EP0400330 B1 EP 0400330B1 EP 90108017 A EP90108017 A EP 90108017A EP 90108017 A EP90108017 A EP 90108017A EP 0400330 B1 EP0400330 B1 EP 0400330B1
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- European Patent Office
- Prior art keywords
- hair
- substance
- developer
- coupler
- ethanol
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
Definitions
- the invention relates to agents for the oxidative dyeing of hair containing a non-sensitizing, non-mutagenic developer substance-coupler substance combination, 2- (2,5-diaminophenyl) ethanol being used as developer substance in combination with certain coupler substances.
- Oxidation dyes have become very important in the field of hair coloring.
- the color is created by the reaction of certain developer substances with certain coupler substances in the presence of an oxidizing agent.
- the currently preferred developer substances are 2,5-diaminotoluene, p-phenylenediamine, 4-aminophenol and 4-amino-3-methylphenol, while a large number of compounds, such as. B. resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-chlororesorcinol, 4,6-dichlororesorcinol, 2-amino-4- (2-hydroxyethyl) aminoanisole, 2- (2,4-diaminophenoxy) ethanol.
- Oxidation dyes which are to be used for coloring human hair, have numerous special requirements.
- the dyes have to be harmless from a toxicological and dermatological point of view and allow coloring in the desired intensity. Furthermore, good light, permanent wave, acid and rub fastness is required for the hair dyeing achieved.
- hair coloring must remain stable for a period of at least four to six weeks without exposure to light, rubbing and chemical agents. It is also necessary that a wide range of different color shades can be produced by combining suitable developer and coupler components.
- the object was therefore to provide oxidation hair colorants on the basis of a well-coloring, but non-sensitizing and non-mutagenic developer substance-coupler substance combination.
- an agent for the oxidative coloring of hair containing a combination of 2- (2,5-diaminophenyl) ethanol as developer substance and at least one coupler substance selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3 , 4-methylenedioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline the task is solved in an excellent manner.
- the 2- (2,5-diaminophenyl) ethanol has been mentioned in the patent literature for some time as a constituent of oxidation hair dyes.
- As a possible component of oxidation hair colorants it is listed, for example, in our own European Offenlegungsschrift 0 166 155 as well as in our own German Offenlegungsschriften 3,625,916, 3,627,398 and 3,706,565, as well as in DE-OS 3 545 371.
- 2- (2,5-diaminophenyl) ethanol falls under a general formula for 1-hydroxyalkyl-2,5-diaminobenzene compounds, which are recommended as developer substances for oxidation hair dyes in our own European patent application 0 007 537.
- the use of the compound 2- (2,5-diaminophenyl) ethanol as developer does not show any differences in the colorations that can be achieved compared to the developer substances 2,5-diaminotoluene and p-phenylenediamine and 2,5-diaminobenzyl alcohol.
- the expected color shades are obtained with the coupler substances according to the invention.
- the fastness properties and the stability of the dyeings are comparable to the fastness properties which are achieved when using 2,5-diaminobenzyl alcohol. In terms of the intensities of the dyeings obtained, the result is even slightly worse.
- 2- (2,5-diaminophenyl) ethanol shows in the Ames mutagenicity test both in the presence and in the absence of hydrogen peroxide, in the chromosome aberration test on CHO cells in vitro (CA test), in the mouse lymphoma test (point mutation in vitro) and no mutagenicity in the Sister Chromatide Exchange test (SCE test), while the developer substance 2,5-diaminobenzyl alcohol has a mutagenic potential in some of these tests.
- a further advantage of the developer substance-coupler substance combination according to the invention becomes evident when the developer substance-coupler substance combination is examined in hair dye mixtures under conditions of use or when colored strands of hair are tested for mutagenic effects in the amestest.
- Another surprising advantage for the developer substance / coupler substance combination according to the invention results from the comparison of colored hair tresses in the Amestest. Hair tresses were used for this experiment, colored on the one hand with a mixture of p-phenylenediamine or 2,5-diaminotoluene as developer substance and various coupler substances and on the other hand with a mixture of 2- (2,5-diaminophenyl) ethanol according to the invention and the same hair color couplers had been.
- Test conditions Hair tresses of 30-50 hairs are impregnated with an agent according to Example 1, in which the coupler substance was in each case contained in an equimolar ratio to the developer substance. The tresses were then kept in a climate cabinet at 40 degrees Celsius for 30 minutes, then rinsed thoroughly with water and finally dried. The hair dyed in this way was then cut into 2.5 cm pieces and used the method of B.N. Ames tested on Salmonella typhimurium strains TA97, TA98 and TA100 in the presence of S9-Mix.
- the developer substance-coupler substance combination according to the invention shows no sensitizing effect in a sensitization test according to the OECD guidelines, either with topical or with intradermal treatment. This surprising finding makes it possible for the first time to provide hair dyes for people with allergies. With the developer substance-coupler substance combinations belonging to the state of the art, on the other hand, the production of high quality non-mutagenic and non-sensitizing hair colorants is not possible.
- the subject of the present application therefore relates to an agent for the oxidative dyeing of hair containing a developer-coupler combination, characterized in that it contains 2- (2,5-diaminophenyl) ethanol or its physiologically compatible, water-soluble developer Lich contains salt, and the coupler substance is selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3,4-methylenedioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline or their physiologically compatible water-soluble salts.
- the developer substances and coupler substances should be contained therein as such or in the form of the physiologically tolerable salts, for example the hydrochlorides or the sulfates.
- the hair colorants according to the invention should contain the 2- (2,5-diaminophenyl) ethanol or its physiologically tolerable salts in an amount sufficient for hair coloring from 0.01 to 4.0 percent by weight, preferably 0.1 to 3.0 percent by weight, the total amount the coupler substances should also be 0.01 to 4.0 percent by weight, preferably 0.1 to 3.0.
- this compound should preferably be contained in the compositions as the only developer substance. If the agents also contain other developer substances, however, it must be ensured that these are also not mutagenic or sensitizing.
- coupler substances may optionally also be contained in a smaller amount to achieve certain color nuances, provided that this does not result in a mutagenic or sensitizing effect of the agent.
- the agent preferably contains only one or more of the above-mentioned coupler substances.
- the coupler substances can each be contained in the hair dye individually or in a mixture with one another.
- the total amount of the developer and coupler substances contained in the hair colorant described here should be 0.01 to 8.0 percent by weight, preferably 0.5 to 6.0 percent by weight.
- the developer substances are generally used in approximately equimolar amounts based on the coupler substances. However, it is not a disadvantage if the developer substance is present in a certain excess or deficit.
- the hair dye of this application can additionally contain other non-sensitizing and non-mutagenic direct-dyeing components, for example 4- (N-ethyl, N-2'-hydroxyethyl) amino-1- (2 "-hydroxyethyl) amino-2-nitrobenzene and 1- (2'-ureidoethyl-amino) -4-nitrobenzene, the amount of these dyes being used is about 0.1 to 4.0 percent by weight.
- other non-sensitizing and non-mutagenic direct-dyeing components for example 4- (N-ethyl, N-2'-hydroxyethyl) amino-1- (2 "-hydroxyethyl) amino-2-nitrobenzene and 1- (2'-ureidoethyl-amino) -4-nitrobenzene, the amount of these dyes being used is about 0.1 to 4.0 percent by weight.
- the coupler and developer substances, as well as the other color components, if they are bases can be in the form of the cosmetically acceptable acid addition salts, for example as hydrochloride or as sulfate or - if they are compounds with phenol or acid groups - in the form of the salts with bases, for example as alkali phenolates.
- the developer substance 2- (2,5-diaminophenyl) ethanol according to the invention can be prepared starting from 2- (2-aminophenyl) ethanol.
- the diacetyl compound obtainable from 2- (2-aminophenyl) ethanol and acetic anhydride is nitrated.
- the resulting mixture of N-acetyl-2- (2-acetoxyethyl) -4-nitroaniline and N-acetyl-2- (2-acetoxyethyl) -5-nitroaniline is saponified with hydrochloric acid.
- the desired 2- (2-amino-5-nitrophenol) ethanol can be separated from it by partial hydrolysis of the hydrochloride.
- the 2- (2,5-diaminophenyl) ethanol is obtained therefrom by catalytic hydrogenation.
- this hair dye are mixed with 50 g hydrogen peroxide solution (6 percent) shortly before use.
- the mixture is then applied to gray hair of people who are sensitized to p-phenylenediamine and p-toluenediamine and left to act at 40 degrees Celsius for 30 minutes. Then it is rinsed with water and dried. The hair is colored black.
- the test subjects allergy sufferers
- 10 g of the above hair dye are mixed with 10 g of hydrogen peroxide solution (6 percent) and the mixture is allowed to act on natural blonde hair at 40 degrees Celsius for 30 minutes. After rinsing with water and drying, the hair is colored in a greenish-ashy natural shade.
Description
Gegenstand der Erfindung sind Mittel zur oxidativen Färbung von Haaren mit einem Gehalt an einer nicht sensibilisierenden nicht mutagenen Entwicklersubstanz-Kupplersubstanz-Kombination, wobei 2-(2,5-Diami- nophenyl)ethanol als Entwicklersubstanz in Kombination mit bestimmten Kupplersubstanzen verwendet wird.The invention relates to agents for the oxidative dyeing of hair containing a non-sensitizing, non-mutagenic developer substance-coupler substance combination, 2- (2,5-diaminophenyl) ethanol being used as developer substance in combination with certain coupler substances.
Auf dem Gebiet der Haarfärbung haben Oxidationsfarbstoffe eine wesentliche Bedeutung erlangt. Die Färbung entsteht hierbei durch Reaktion bestimmter Entwicklersubstanzen mit bestimmten Kupplersubstanzen in Gegenwart eines Oxidationsmittels.Oxidation dyes have become very important in the field of hair coloring. The color is created by the reaction of certain developer substances with certain coupler substances in the presence of an oxidizing agent.
Die derzeit bevorzugt eingesetzten Entwicklersubstanzen sind 2,5-Diaminotoluol, p-Phenylendiamin, 4-Aminophenol und 4-Amino-3-methylphenol, während als Kupplersubstanzen eine Vielzahl von Verbindungen, wie z. B. Resorcin, 2-Methylresorcin, 4-Chlorresorcin, 2-Chlorresorcin, 4,6-Dichlorresorcin, 2-Amino-4-(2-hydroxyethyl)aminoanisol, 2-(2,4-Diaminophenoxy)ethanol. 1-Naphthol, m-Phenylendiamin, 5-Amino-2-methylphenol, 3-Amino-4-chlor-6-methylphenol, 3-Amino-2-methylphenol, 2-(4-Amino-2-hydroxyphenoxy) ethanol, 4-Amino-1,2-methylendioxybenzol, 2,4-Diamino-5-ethoxytoluol, 4-Hydroxyindol, 3-Amino-5-hydroxy-2,6-dimethoxypyridin, 3,5-Diamino-2,6-dimethoxypyridin, 3-Amino-6-methoxy-2-methylaminopyridin, Thymol, 2-(2-Hydroxyethyl)-5-methylphenol, 2-Hydroxymethyl-5-methylphenol, 3-Aminophenol und N-(2-Hydroxyethyl)-3,4-methylendioxyanilin, verwendet werden.The currently preferred developer substances are 2,5-diaminotoluene, p-phenylenediamine, 4-aminophenol and 4-amino-3-methylphenol, while a large number of compounds, such as. B. resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 2-chlororesorcinol, 4,6-dichlororesorcinol, 2-amino-4- (2-hydroxyethyl) aminoanisole, 2- (2,4-diaminophenoxy) ethanol. 1-naphthol, m-phenylenediamine, 5-amino-2-methylphenol, 3-amino-4-chloro-6-methylphenol, 3-amino-2-methylphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 4 -Amino-1,2-methylenedioxybenzene, 2,4-diamino-5-ethoxytoluene, 4-hydroxyindole, 3-amino-5-hydroxy-2,6-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 3 -Amino-6-methoxy-2-methylaminopyridine, thymol, 2- (2-hydroxyethyl) -5-methylphenol, 2-hydroxymethyl-5-methylphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline , be used.
An Oxidationsfarbstoffe, die zur Färbung menschlicher Haare verwendet werden sollen, sind zahlreiche besondere Anforderungen gestellt. Die Farbstoffe müssen in toxikologischer und dermatologischer Hinsicht unbedenklich sein und Färbungen in der gewünschten Intensität ermöglichen. Ferner wird für die erzielten Haarfärbungen eine gute Licht-, Dauerwell-, Säure- und Reibeechtheit gefordert.Oxidation dyes, which are to be used for coloring human hair, have numerous special requirements. The dyes have to be harmless from a toxicological and dermatological point of view and allow coloring in the desired intensity. Furthermore, good light, permanent wave, acid and rub fastness is required for the hair dyeing achieved.
In jedem Fall müssen solche Haarfärbungen ohne Einwirkung von Licht, Reibung und chemischen Mitteln über einen Zeitraum von mindestens vier bis sechs Wochen stabil bleiben. Außerdem ist es erforderlich, daß durch Kombination geeigneter Entwickler- und Kupplerkomponenten eine breite Palette verschiedener Farbnuancen erzeugt werden kann.In any case, such hair coloring must remain stable for a period of at least four to six weeks without exposure to light, rubbing and chemical agents. It is also necessary that a wide range of different color shades can be produced by combining suitable developer and coupler components.
Gegen die zur Zeit hauptsächlich eingesetzten Entwicklersubstanzen p-Phenylendiamin, 2,5-Diaminotoluol und 4-Aminophenol wurden in letzter Zeit Bedenken bezuglich ihrer physiologischen Verträglichkeit erhoben. Ein Problem stellt dabei die Sensibilisierung bestimmter Personen auf p-Phenylendiaminderivate dar (Paraallergiker). Diesem Personenkreis war es bisher nicht möglich, sich die Haare mit Haarfärbemitteln auf der Basis von p-Phenylendiaminderivaten färben zu lassen. Weiterhin ist nicht nur die sensibilisierende Wirkung der reinen Entwicklersubstanzen, sondern auch die der Mischungen mit Kupplersubstanzen sowie die der daraus gebildeten Farbstoffe zu berücksichtigen.Concerns about the physiologically tolerated development substances p-phenylenediamine, 2,5-diaminotoluene and 4-aminophenol have been raised lately. One problem is the sensitization of certain people to p-phenylenediamine derivatives (people with allergies). It has not been possible for this group of people to have their hair dyed with p-phenylenediamine derivatives. Furthermore, not only the sensitizing effect of the pure developer substances, but also that of the mixtures with coupler substances and that of the dyes formed therefrom must be taken into account.
Mit der Bereitstellung von Pyrimidinderivaten als Entwicklersubstanzen wurden zwar die toxikologischen Probleme gemindert, aber diese Verbindungen können in färberischer Hinsicht nicht völlig zufriedenstellen.The provision of pyrimidine derivatives as developer substances has alleviated the toxicological problems, but these compounds cannot be completely satisfactory from a coloring point of view.
Es bestand daher die Aufgabe, Oxidationshaarfärbemittel auf der Basis einer gut färbenden, jedoch nicht sensibilisierenden und nicht mutagenen Entwicklersubstanz-Kupplersubstanz-Kombination zur Verfügung zu stellen.The object was therefore to provide oxidation hair colorants on the basis of a well-coloring, but non-sensitizing and non-mutagenic developer substance-coupler substance combination.
Hierzu wurde nun überraschend gefunden, daß durch ein Mittel zur oxidativen Färbung von Haaren mit einem Gehalt einer Kombination aus 2-(2,5-Diaminophenyl)ethanol als Entwicklersubstanz und mindestens einer Kupplersubstanz ausgewählt aus Resorcin, 2-Methylresorcin, 4-Chlorresorcin, 3,4-Methylendioxyphenol, 3-Aminophenol und N-(2-Hydroxyethyl)-3,4-methylendioxyanilin die gestellte Aufgabe in hervorragender Weise gelöst wird.It has now surprisingly been found that an agent for the oxidative coloring of hair containing a combination of 2- (2,5-diaminophenyl) ethanol as developer substance and at least one coupler substance selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3 , 4-methylenedioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline the task is solved in an excellent manner.
Das 2-(2,5-Diaminophenyl)ethanol wird seit einiger Zeit als Bestandteil von Oxidationshaarfärbemitteln in der Patentliteratur erwähnt. Als möglicher Bestandteil von Oxidationshaarfärbemitteln ist es zum Beispiel in der eigenen europäischen Offenlegungsschrift 0 166 155 sowie in den eigenen deutschen Offenlegungsschriften 3 625 916, 3 627 398 und 3 706 565 sowie auch in der DE-OS 3 545 371 aufgeführt. Ferner fällt das 2-(2,5-Diaminophenyl)ethanol unter eine allgemeine Formel für 1-Hydroxyalkyl-2,5-diaminobenzolverbindun- gen, welche als Entwicklersubstanzen für Oxidationshaarfärbemittel in der eigenen europäischen Offenlegungsschrift 0 007 537 empfohlen werden. Die dort mehrfach konkret genannte Verbindung 1-Hydroxymethyl-2,5-diaminobenzol (2,5Diaminobenzylalkohol) hat sich jedoch als sensibilisierend erwiesen. Die ausgezeichnete Eignung der Entwicklersubstanz 2-(2,5-Diaminophenyl)ethanol in Kombination mit den vorstehend genannten Kupplersubstanzen zur Lösung der gestellten Aufgabe wurde bisher nicht erkannt. Dementsprechend sind die erfindungsgemäßen EntwicklersubstanzKupplersubstanz-Kombinationen in keiner dieser Druckschriften beschrieben.The 2- (2,5-diaminophenyl) ethanol has been mentioned in the patent literature for some time as a constituent of oxidation hair dyes. As a possible component of oxidation hair colorants, it is listed, for example, in our own European Offenlegungsschrift 0 166 155 as well as in our own German Offenlegungsschriften 3,625,916, 3,627,398 and 3,706,565, as well as in DE-OS 3 545 371. Furthermore, 2- (2,5-diaminophenyl) ethanol falls under a general formula for 1-hydroxyalkyl-2,5-diaminobenzene compounds, which are recommended as developer substances for oxidation hair dyes in our own European patent application 0 007 537. However, the compound 1-hydroxymethyl-2,5-diaminobenzene (2,5-diaminobenzyl alcohol), which has been specifically mentioned there several times, has proven to be a sensitizer. The excellent suitability of the developer substance 2- (2,5-diaminophenyl) ethanol in combination with the above-mentioned coupler substances to solve the problem has not been recognized so far. Accordingly, the developer substance-coupler substance combinations according to the invention are not described in any of these publications.
Die konkrete Darstellung des 2-(2,5-Diaminophenyl)ethanols ist bisher ebenfalls weder beschrieben noch hat diese Entwicklersubstanz Eingang in die Haarfärbepraxis gefunden. Wegen der inzwischen festgestellten sensibilisierenden Eigenschaften der aus der europäischen Offenlegungsschrift 0 007 537 bekannten homologen Verbindung 2,5-Diaminobenzylalkohol mußte eine Synthese dieser Verbindung auch nicht lohnend erscheinen.The concrete representation of 2- (2,5-diaminophenyl) ethanol has also not been described so far, nor has this developer substance found its way into hair dyeing practice. Because of the sensitizing properties of the homologous compound 2,5-diaminobenzyl alcohol known from European Patent Application 0 007 537, which has now been established, a synthesis of this compound did not have to be worthwhile either seem to be.
Die Verwendung der Verbindung 2-(2,5-Diaminophenyl)ethanol als Entwicklersubstanz zeigt bezüglich der erzielbaren Färbungen keine Unterschiede gegenüber den üblicherweise eingesetzten Entwicklersubstanzen 2,5-Diaminotoluol und p-Phenylendiamin sowie dem 2,5-Diaminobenzylalkohol. Mit den erfindungsgemäßen Kupplersubstanzen werden die erwarteten Farbtöne erhalten. Die Echtheiten und die Stabilität der Färbungen sind vergleichbar mit den Echtheiten, die bei der Verwendung von 2,5-Diaminobenzylalkohol erzielt werden. Bezüglich der Intensitäten der erhaltenen Färbungen ist sogar ein geringfügig schlechteres Ergebnis festzustellen.The use of the compound 2- (2,5-diaminophenyl) ethanol as developer does not show any differences in the colorations that can be achieved compared to the developer substances 2,5-diaminotoluene and p-phenylenediamine and 2,5-diaminobenzyl alcohol. The expected color shades are obtained with the coupler substances according to the invention. The fastness properties and the stability of the dyeings are comparable to the fastness properties which are achieved when using 2,5-diaminobenzyl alcohol. In terms of the intensities of the dyeings obtained, the result is even slightly worse.
Der große und überraschende technische Fortschritt, der bei der Verwendung von 2-(2,5-Diaminophe- nyl)ethanol mit den vorstehend genannten Kupplersubstanzen erzielt werden kann, liegt vielmehr in den physiologischen Eigenschaften begründet. So zeigt das 2-(2,5-Diaminophenyl)ethanol im Mutagenitätstest nach Ames sowohl in Anwesenheit als auch in Abwesenheit von Wasserstoffperoxid, im Chromosomenaberrationstest an CHO-Zellen in vitro (CA-Test), im Mouse Lymphoma Test (Punktmutation in vitro) und im Sister-Chromatide-Exchange-Test (SCE-Test) keinerlei Mutagenität, während die Entwicklersubstanz 2,5-Diaminobenzylalkohol in einigen dieser Teste ein mutagenes Potential aufweist.The great and surprising technical progress that can be achieved with the use of 2- (2,5-diaminophenyl) ethanol with the above-mentioned coupler substances is rather due to the physiological properties. For example, 2- (2,5-diaminophenyl) ethanol shows in the Ames mutagenicity test both in the presence and in the absence of hydrogen peroxide, in the chromosome aberration test on CHO cells in vitro (CA test), in the mouse lymphoma test (point mutation in vitro) and no mutagenicity in the Sister Chromatide Exchange test (SCE test), while the developer substance 2,5-diaminobenzyl alcohol has a mutagenic potential in some of these tests.
Ein weiterer Vorteil der erfindungsgemäßen Entwicklersubstanz-Kupplersubstanz-Kombination wird offenkundig, wenn die Entwicklersubstanz-Kupplersubstanz-Kombination in Haarfärbegemischen unter Anwendungsbedingungen oder wenn gefärbte Haarsträhnen im Amestest auf mutagene Wirkung untersucht werden.A further advantage of the developer substance-coupler substance combination according to the invention becomes evident when the developer substance-coupler substance combination is examined in hair dye mixtures under conditions of use or when colored strands of hair are tested for mutagenic effects in the amestest.
Der Vergleich von Haarfärbelösungen, die die Entwicklersubstanz p-Phenylendiamin, 2,5-Diaminotoluol oder 2-(2,5-Diaminophenyl)ethanol enthalten, unter oxidativen Bedingungen im Amestest zeigt, daß die allgemein verwendeten Entwicklersubstanzen ein mutagenes Potential zeigen, während die erfindungsgemäße Entwicklersubstanz 2-(2,5-Diaminophenyl)ethanol nicht mutagen wirkt.The comparison of hair dye solutions containing the developer substance p-phenylenediamine, 2,5-diaminotoluene or 2- (2,5-diaminophenyl) ethanol under oxidative conditions in the amestest shows that the developer substances generally used show a mutagenic potential, while those according to the invention Developer substance 2- (2,5-diaminophenyl) ethanol is not mutagenic.
Ein weiterer, überraschender Vorteil für die erfindungsgemäße Entwicklersubstanz/Kupplersubstanz-Kombination ergibt sich aus dem Vergleich von gefärbten Haarsträhnchen im Amestest. Für diesen Versuch wurden Haarsträhnchen verwendet, die einerseits mit einer Mischung aus p-Phenylendiamin oder 2,5-Diaminotoluol als Entwicklersubstanz und verschiedenen Kupplersubstanzen und andererseits mit einer Mischung aus dem erfindungsgemäßen 2-(2,5-Diaminophenyl)ethanol und den gleichen Haarfarbkupplern eingefärbt worden waren.Another surprising advantage for the developer substance / coupler substance combination according to the invention results from the comparison of colored hair tresses in the Amestest. Hair tresses were used for this experiment, colored on the one hand with a mixture of p-phenylenediamine or 2,5-diaminotoluene as developer substance and various coupler substances and on the other hand with a mixture of 2- (2,5-diaminophenyl) ethanol according to the invention and the same hair color couplers had been.
Die Ergebnisse dieser Versuche zeigt die nachfolgende Tabelle 1:
Versuchsbedingungen: Haarsträhnchen aus 30-50 Haaren werden mit einem Mittel nach Beispiel 1, bei dem die Kupplersubstanz jeweils im äquimolaren Verhältnis zur Entwicklersubstanz enthalten war, getränkt. Die Strähnen wurden anschließend 30 Minuten lang bei 40 Grad Celsius im Klimaschrank aufbewahrt, sodann gründlich mit Wasser gespült und schließlich getrocknet. Die so gefärbten Haar wurden nun im 2,5 cm lange Stücke geschnitten und nach der Methodik von B.N. Ames an Salmonella typhimurium-Stämmen TA97, TA98 und TA100 in Anwesenheit von S9-Mix geprüft.Test conditions: Hair tresses of 30-50 hairs are impregnated with an agent according to Example 1, in which the coupler substance was in each case contained in an equimolar ratio to the developer substance. The tresses were then kept in a climate cabinet at 40 degrees Celsius for 30 minutes, then rinsed thoroughly with water and finally dried. The hair dyed in this way was then cut into 2.5 cm pieces and used the method of B.N. Ames tested on Salmonella typhimurium strains TA97, TA98 and TA100 in the presence of S9-Mix.
Wie die Ergebnisse zeigen, ist im Gegensatz zu Kombinationen aus 2,5-Diaminotoluol oder p-Phenylendiamin und den vorstehend genannten Kupplersubstanzen kein mutagenes Potential der mit der erfindungsgemäßen Kombination gefärbten Haarsträhnchen vorhanden.As the results show, in contrast to combinations of 2,5-diaminotoluene or p-phenylenediamine and the above-mentioned coupler substances, there is no mutagenic potential in the hair highlights colored with the combination according to the invention.
Weiterhin zeigt die erfindungsgemäße Entwicklersubstanz-Kupplersubstanz-Kombination in einem Sensibilisierungstest gemäß den OECD-Richtlinien sowohl bei topischer als auch bei intradermaler Behandlung keine sensibilisierende Wirkung. Dieser überraschende Befund ermöglicht es erstmals, Haarfärbemittel für Paraallergiker bereitzustellen. Mit den zum Stand der Technik gehörenden Entwicklersubstanz-Kupplersubstanz-Kombinationen ist dagegen die Herstellung von qualitativ hochwertigen nicht mutagenen und nicht sensibilisierenden Haarfärbemitteln nicht möglich.Furthermore, the developer substance-coupler substance combination according to the invention shows no sensitizing effect in a sensitization test according to the OECD guidelines, either with topical or with intradermal treatment. This surprising finding makes it possible for the first time to provide hair dyes for people with allergies. With the developer substance-coupler substance combinations belonging to the state of the art, on the other hand, the production of high quality non-mutagenic and non-sensitizing hair colorants is not possible.
Der Gegenstand der vorliegenden Anmeldung betrifft daher ein Mittel zur oxidativen Färbung von Haaren mit einem Gehalt an einer Entwicklersubstanz-Kupplersubstanz-Kombination, dadurch gekennzeichnet, daß es als Entwicklersubstanz 2-(2,5-Diaminophenyl)ethanol oder dessen physiologisch verträgliches, wasserlösliches Salz enthält, und die Kupplersubstanz ausgewählt ist aus Resorcin, 2-Methylresorcin, 4-Chlorresorcin, 3,4-Methylendioxyphenol, 3-Aminophenol und N-(2-Hydroxyethyl)-3,4-methylendioxyanilin oder deren physiologisch verträglichen wasserlöslichen Salzen.The subject of the present application therefore relates to an agent for the oxidative dyeing of hair containing a developer-coupler combination, characterized in that it contains 2- (2,5-diaminophenyl) ethanol or its physiologically compatible, water-soluble developer Lich contains salt, and the coupler substance is selected from resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 3,4-methylenedioxyphenol, 3-aminophenol and N- (2-hydroxyethyl) -3,4-methylenedioxyaniline or their physiologically compatible water-soluble salts.
Die Entwicklersubstanzen und Kupplersubstanzen sollen darin als solche oder in Form des physiologisch verträglichen Salze, beispielsweise der Hydrochloride oder der Sulfate, enthalten sein.The developer substances and coupler substances should be contained therein as such or in the form of the physiologically tolerable salts, for example the hydrochlorides or the sulfates.
Die erfindungsgemäßen Haarfärbemittel sollen das 2-(2,5-Diaminophenyl)ethanol oder dessen physiologisch verträgliche Salze in einer für die Haarfärbung ausreichenden Menge von 0,01 bis 4,0 Gewichtsprozent, vorzugsweise 0,1 bis 3,0 Gewichtsprozent enthalten, die Gesamtmenge der Kupplersubstanzen soll ebenfalls 0,01 bis 4,0 Gewichtsprozent, vorzugsweise 0,1 bis 3,0 betragen.The hair colorants according to the invention should contain the 2- (2,5-diaminophenyl) ethanol or its physiologically tolerable salts in an amount sufficient for hair coloring from 0.01 to 4.0 percent by weight, preferably 0.1 to 3.0 percent by weight, the total amount the coupler substances should also be 0.01 to 4.0 percent by weight, preferably 0.1 to 3.0.
Aufgrund der vorteilhaften Eigenschaften des erfindungsgemäßen 2-(2,5-Diaminophenyl)ethanols soll diese Verbindung vorzugsweise als einzige Entwicklersubstanz in den Mitteln enthalten sein. Falls die Mittel noch andere Entwicklersubstanzen enthalten, muß jedoch gewährleistet sein, daß diese ebenfalls nicht mutagen oder sensibilisierend sind.Because of the advantageous properties of the 2- (2,5-diaminophenyl) ethanol according to the invention, this compound should preferably be contained in the compositions as the only developer substance. If the agents also contain other developer substances, however, it must be ensured that these are also not mutagenic or sensitizing.
Neben den vorstehend genannten erfindungsgemäß verwendeten Kupplersubstanzen können zur Erzielung gewisser Farbnuancen gegebenenfalls zusätzlich noch weitere Kupplersubstanzen in geringerer Menge enhalten sein, sofern dadurch keine mutagene oder sensibilisierende Wirkung des Mittels auftritt. Vorzugsweise enthält das Mittel jedoch ausschließlich eine oder mehrere der vorstehend genannten Kupplersubstanzen. Die Kupplersubstanzen können in dem Haarfärbemittel jeweils einzeln oder im Gemisch miteinander enthalten sein. Die Gesamtmenge der in dem hier beschriebenen Haarfärbemittel enthaltenen Entwickler- und Kupplersubstanzen soll 0,01 bis 8,0 Gewichtsprozent, vorzugsweise 0,5 bis 6,0 Gewichtsprozent betragen.In addition to the above-mentioned coupler substances used according to the invention, additional coupler substances may optionally also be contained in a smaller amount to achieve certain color nuances, provided that this does not result in a mutagenic or sensitizing effect of the agent. However, the agent preferably contains only one or more of the above-mentioned coupler substances. The coupler substances can each be contained in the hair dye individually or in a mixture with one another. The total amount of the developer and coupler substances contained in the hair colorant described here should be 0.01 to 8.0 percent by weight, preferably 0.5 to 6.0 percent by weight.
Die Entwicklersubstanzen werden im allgemeinen in etwa äquimolaren Mengen bezogen auf die Kupplersubstanzen eingesetzt. Es ist jedoch nicht von Nachteil, wenn die Entwicklersubstanz in einem gewissen Überschuß oder Unterschuß vorhanden ist.The developer substances are generally used in approximately equimolar amounts based on the coupler substances. However, it is not a disadvantage if the developer substance is present in a certain excess or deficit.
Weiterhin kann das Haarfärbemittel dieser Anmeldung zusätzlich andere nicht sensibilisierende und nicht mutagene direktfärbende Farbkomponenten, beispielsweise 4-(N-Ethyl,N-2'-hydroxyethyl)amino-1-(2"-hydroxyethyl)-amino-2-nitrobenzol und 1-(2'-Ureidoethyl-amino)-4-nitrobenzol, enthalten, wobei die Einsatzmenge dieser Farbstoffe etwa 0,1 bis 4,0 Gewichtsprozent beträgt.Furthermore, the hair dye of this application can additionally contain other non-sensitizing and non-mutagenic direct-dyeing components, for example 4- (N-ethyl, N-2'-hydroxyethyl) amino-1- (2 "-hydroxyethyl) amino-2-nitrobenzene and 1- (2'-ureidoethyl-amino) -4-nitrobenzene, the amount of these dyes being used is about 0.1 to 4.0 percent by weight.
Selbstverständlich können die Kuppler- und Entwicklersubstanzen sowie die anderen Farbkomponenten, sofern es sich um Basen handelt, in Form der kosmetisch verträglichen Säureadditionssalze, beispielsweise als Hydrochlorid oder als Sulfat oder- sofern es sich um Verbindungen mit Phenol- oder Säuregruppen handelt - in Form der Salze mit Basen, zum Beispiel als Alkaliphenolate, eingesetzt werden.Of course, the coupler and developer substances, as well as the other color components, if they are bases, can be in the form of the cosmetically acceptable acid addition salts, for example as hydrochloride or as sulfate or - if they are compounds with phenol or acid groups - in the form of the salts with bases, for example as alkali phenolates.
Die erfindungsgemäße Entwicklersubstanz 2-(2,5-Diaminophenyl)ethanol kann ausgehend von 2-(2-Aminophenyl)ethanol hergestellt werden. Dabei wird die aus 2-(2-Aminophenyl)ethanol und Essigsäureanhydrid erhältliche Diacetylverbindung nitriert. Die erhaltene Mischung von N-Acetyl-2-(2-acetoxyethyl)-4-nitroanilin und N-Acetyl-2-(2-acetoxyethyl)-5-nitroanilin wird mit Salzsäure verseift. Das gewünschte 2-(2-Amino-5-nitrophenol)ethanol kann daraus durch partielle Hydrolyse der Hydrochloride abgetrennt werden. Das 2-(2,5-Diaminophenyl)ethanol wird daraus durch katalytische Hydrierung erhalten.The developer substance 2- (2,5-diaminophenyl) ethanol according to the invention can be prepared starting from 2- (2-aminophenyl) ethanol. The diacetyl compound obtainable from 2- (2-aminophenyl) ethanol and acetic anhydride is nitrated. The resulting mixture of N-acetyl-2- (2-acetoxyethyl) -4-nitroaniline and N-acetyl-2- (2-acetoxyethyl) -5-nitroaniline is saponified with hydrochloric acid. The desired 2- (2-amino-5-nitrophenol) ethanol can be separated from it by partial hydrolysis of the hydrochloride. The 2- (2,5-diaminophenyl) ethanol is obtained therefrom by catalytic hydrogenation.
In der nachstehenden Beispielen soll der Gegenstand der Erfindung näher erläutert werden, ohne ihn auf die Beispiele zu beschränken.The subject matter of the invention is to be explained in more detail in the examples below, without restricting it to the examples.
Man vermischt kurz vor dem Gebrauch 50 g des vorstehenden Haarfärbemittels mit 50 g Wasserstoffperoxidlösung (6-prozentig) und läßt das Gemisch 30 Minuten lang auf weiße Naturhaare einwirken. Danach wird das Haar mit Wasser gespült und getrocknet. Das Haar hat einen natürlichen, dunkelblonden Farbton angenommen.Shortly before use, 50 g of the above hair dye are mixed with 50 g of hydrogen peroxide solution (6 percent) and the mixture is allowed to act on white natural hair for 30 minutes. Then the hair is rinsed with water and dried. The hair has taken on a natural, dark blonde shade.
Man vermischt kurz vor dem Gebrauch 10 g des vorstehenden Haarfärbemittels mit 10 g Wasserstoffperoxidlösung (6-prozentig) und läßt die Mischung 30 Minuten lang bei 40 Grad Celsius auf blonde Naturhaare einwirken. Nach dem Spülen mit Wasser und dem Trocknen ist das Haar in einem grünlich aschigen Naturton gefärbt.Shortly before use, 10 g of the above hair dye are mixed with 10 g of hydrogen peroxide solution (6 percent) and the mixture is allowed to act on natural blonde hair at 40 degrees Celsius for 30 minutes. After rinsing with water and drying, the hair is colored in a greenish-ashy natural shade.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3917304A DE3917304A1 (en) | 1989-05-27 | 1989-05-27 | OXIDATION HAIR COLORING AGENTS |
| DE3917304 | 1989-05-27 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0400330A1 EP0400330A1 (en) | 1990-12-05 |
| EP0400330B1 true EP0400330B1 (en) | 1993-03-10 |
| EP0400330B2 EP0400330B2 (en) | 2001-03-07 |
Family
ID=6381521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90108017A Expired - Lifetime EP0400330B2 (en) | 1989-05-27 | 1990-04-27 | Oxidation hair dyes |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0400330B2 (en) |
| AT (1) | AT402787B (en) |
| BE (1) | BE1002856A4 (en) |
| DE (2) | DE3917304A1 (en) |
| ES (1) | ES2055214T5 (en) |
| FR (1) | FR2647341B1 (en) |
| GB (1) | GB2239265B (en) |
| RU (1) | RU2060728C1 (en) |
| WO (1) | WO1990014818A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07330558A (en) * | 1994-06-06 | 1995-12-19 | L'oreal Sa | Oxidative dye composition for keratin fiber made of 2-(beta-hydroxyethyl)-para-phenylene diamine,2-methyl resorcinol, and 3-aminophenol and dyeing method using it |
| EP0688558A2 (en) * | 1994-06-21 | 1995-12-27 | L'oreal | Composition for dyeing keratinous fibres comprising 2-(beta-hydroxyethyl)-paraphenylene-diamine, 2-methylresorcin and resorcin |
| JPH0834716A (en) * | 1994-01-24 | 1996-02-06 | L'oreal Sa | Composition for oxidation dyeing of keratin fiber containingpara-phenylenediamine derivative and 2-methyl-5-aminophenol and method for dyeing using said composition |
| JPH0834715A (en) * | 1994-01-24 | 1996-02-06 | L'oreal Sa | Composition for oxidation dyeing of keratin fiber containingpara-phenylenediamine derivative and meta-aminophenol derivative and method for dyeing using said composition |
| JPH0834713A (en) * | 1994-01-24 | 1996-02-06 | L'oreal Sa | Composition for oxidation dyeing of keratin fiber containing para-phenylenediamine derivative and meta-phenylenediamine derivative and method for dyeing usingsaid composition |
| EP0776652A1 (en) | 1995-11-30 | 1997-06-04 | GOLDWELL GmbH | Oxidation hair dyes containing at least one plant extract |
| US5735908A (en) * | 1994-03-21 | 1998-04-07 | L'oreal | Compositions and processes for the oxidative dyeing of keratin fibres with para-phenylenediamine derivatives and a cationic substantive polymer |
| EP0857478A2 (en) * | 1997-02-08 | 1998-08-12 | GOLDWELL GmbH | Oxidative hair dye |
| EP0857479A2 (en) * | 1997-02-08 | 1998-08-12 | GOLDWELL GmbH | Oxidative hair dye |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4417546A1 (en) * | 1994-05-19 | 1995-11-23 | Henkel Kgaa | 2-oxoacetic acid derivatives for dyeing keratin fibers |
| FR2720275B1 (en) * | 1994-05-26 | 1996-07-05 | Oreal | Keratin fiber oxidation dyeing composition comprising a paraphenylenediamine derivative and a 6-hydroxy 1,4-benzoxazine, and dyeing process using such a composition. |
| DE4436743A1 (en) * | 1994-10-14 | 1996-04-18 | Wella Ag | Oxidation hair dye |
| FR2726185B1 (en) * | 1994-11-02 | 1997-04-25 | Oreal | TINCTORIAL COMPOSITION BASED ON OXIDATION DYES AND DYEING METHOD USING THE SAME |
| DE4440957A1 (en) * | 1994-11-17 | 1996-05-23 | Henkel Kgaa | Oxidation dye |
| DE19505634C2 (en) * | 1995-02-18 | 1998-04-16 | Wella Ag | Means and methods for oxidative coloring of hair |
| DE19535340A1 (en) | 1995-09-22 | 1997-03-27 | Henkel Kgaa | An oxidation |
| DE19621499C2 (en) * | 1996-05-29 | 1998-04-09 | Goldwell Gmbh | Hair Dye |
| DE19645538A1 (en) * | 1996-11-05 | 1998-05-07 | Wella Ag | Colorants for coloring keratin fibers |
| FR2769910B1 (en) | 1997-10-22 | 2001-06-15 | Oreal | PROCESS FOR THE SYNTHESIS OF 2-HYDROXYALKYL PARAPHENYLENEDIAMINES, NEW 2-HYDROXYALKYL PARAPHENYLENEDIAMINES, THEIR USE FOR OXIDATION DYE, TINCTORIAL COMPOSITIONS AND DYEING PROCESSES |
| CA2254413C (en) * | 1997-11-19 | 2006-12-19 | Bristol-Myers Squibb Company | Dye compositions |
| US5993491A (en) * | 1998-05-13 | 1999-11-30 | Bristol-Myers Squibb Company | Oxidative hair dye compositions and methods containing 1-(4-aminophenyl)-2-pyrrolidinemethanols |
| DE19828205C1 (en) * | 1998-06-25 | 1999-11-25 | Goldwell Gmbh | Oxidation hair dyeing system giving e.g. blue and violet colors with peroxide |
| US6228130B1 (en) | 1998-11-03 | 2001-05-08 | Bristol-Myers Squibb Company | Primary intermediate in oxidative hair dyeing |
| US6342079B1 (en) * | 2000-01-27 | 2002-01-29 | Bristol-Myers Squibb Company | Primary intermediate for use in oxidative hair dyeing |
| US6521761B2 (en) | 2000-12-06 | 2003-02-18 | Clairol Incorporated | Primary intermediates for oxidative coloration of hair |
| DE10113027A1 (en) | 2001-03-17 | 2002-09-19 | Wella Ag | 3-Diaminophenyl-acrylamide derivatives or their physiologically acceptable, water-soluble salts, used as developers in combination with couplers in oxidative dye formulations, especially for dyeing hair are new |
| WO2013144260A2 (en) | 2012-03-30 | 2013-10-03 | L'oreal | Composition comprising (2,5-diaminophenyl)ethanol, an alkylpolyglucoside nonionic surfactant, an oxyethylenated sorbitan ester or a polyalkoxylated or polyglycerolated fatty alcohol in a medium rich in fatty substances, dyeing process and device therefore |
| RU2541811C1 (en) * | 2013-12-12 | 2015-02-20 | Общество с ограниченной ответственностью "ЮНИКОСМЕТИК" | Hair-dying composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2831847A1 (en) * | 1978-07-20 | 1980-02-07 | Wella Ag | AGENTS FOR COLORING HAIR |
| DE3423933A1 (en) † | 1984-06-29 | 1986-01-09 | Wella Ag, 6100 Darmstadt | 2-ALKYLSUFONYL-1,4-DIAMINOBENZOLES, METHOD FOR THE PRODUCTION THEREOF AND OXIDATION HAIR COLORING AGENTS WITH A CONTENT OF THESE COMPOUNDS |
| DE3430513A1 (en) * | 1984-08-18 | 1986-02-27 | Wella Ag, 6100 Darmstadt | HAIR DYE WITH DIAMINO-TETRAFLUORETHOXYBENZENE AND NEW DIAMINO-TETRAFLUORETHOXYBENZENE |
| LU85705A1 (en) † | 1984-12-21 | 1986-07-17 | Oreal | TINCTORIAL HAIR COMPOSITION BASED ON OXIDATION DYES AND XANTHANE GUM |
| DE3625916A1 (en) † | 1986-07-31 | 1988-02-04 | Wella Ag | OXIDATION HAIR COLORING AGENT BASED ON A GEL-SHAPED WEIGHT AND METHOD FOR COLORING HAIR |
| DE3627398A1 (en) * | 1986-08-13 | 1988-02-18 | Wella Ag | Composition and process for the oxidative dyeing of hair using 3-(2',2',2'-trifluoroethyl)aminophenol and preparation thereof |
| DE3706565A1 (en) * | 1987-02-28 | 1988-09-08 | Wella Ag | Composition and method for the dyeing of hair using 3,5-diaminopyridine derivatives, and novel 3,5-diaminopyridine derivatives |
-
1989
- 1989-05-27 DE DE3917304A patent/DE3917304A1/en not_active Withdrawn
-
1990
- 1990-04-27 WO PCT/EP1990/000677 patent/WO1990014818A1/en unknown
- 1990-04-27 RU SU904894549A patent/RU2060728C1/en not_active IP Right Cessation
- 1990-04-27 DE DE9090108017T patent/DE59000997D1/en not_active Expired - Lifetime
- 1990-04-27 ES ES90108017T patent/ES2055214T5/en not_active Expired - Lifetime
- 1990-04-27 EP EP90108017A patent/EP0400330B2/en not_active Expired - Lifetime
- 1990-04-27 AT AT0900790A patent/AT402787B/en not_active IP Right Cessation
- 1990-05-23 FR FR9006429A patent/FR2647341B1/en not_active Expired - Lifetime
- 1990-05-23 BE BE9000547A patent/BE1002856A4/en not_active IP Right Cessation
- 1990-12-21 GB GB9028046A patent/GB2239265B/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2601641B2 (en) * | 1994-01-24 | 1997-04-16 | ロレアル | Composition for oxidative dyeing of keratin fibers, containing a para-phenylenediamine derivative and a meta-phenylenediamine derivative, and a dyeing method using the composition |
| JPH0834716A (en) * | 1994-01-24 | 1996-02-06 | L'oreal Sa | Composition for oxidation dyeing of keratin fiber containingpara-phenylenediamine derivative and 2-methyl-5-aminophenol and method for dyeing using said composition |
| JPH0834715A (en) * | 1994-01-24 | 1996-02-06 | L'oreal Sa | Composition for oxidation dyeing of keratin fiber containingpara-phenylenediamine derivative and meta-aminophenol derivative and method for dyeing using said composition |
| JPH0834713A (en) * | 1994-01-24 | 1996-02-06 | L'oreal Sa | Composition for oxidation dyeing of keratin fiber containing para-phenylenediamine derivative and meta-phenylenediamine derivative and method for dyeing usingsaid composition |
| US5529584A (en) * | 1994-01-24 | 1996-06-25 | L'oreal | Composition for the oxidation dyeing of keratinous fibres, comprising a para-phenylenediamine derivative and 2-methyl-5-aminophenol, and dyeing process using such a composition |
| US5538516A (en) * | 1994-01-24 | 1996-07-23 | L'oreal | Composition for the oxidation dyeing of keratinous fibres, comprising a para-phenylenediamine derivative and a meta-aminophenol derivative, and dyeing process using such a composition |
| US6554870B1 (en) | 1994-03-21 | 2003-04-29 | L'oreal | Composition for the oxidation dyeing of keratin fibres comprising a para-phenylenediamine derivative and a cationic or amphoteric substantive polymer, and the use thereof |
| US5735908A (en) * | 1994-03-21 | 1998-04-07 | L'oreal | Compositions and processes for the oxidative dyeing of keratin fibres with para-phenylenediamine derivatives and a cationic substantive polymer |
| JP2582235B2 (en) * | 1994-06-06 | 1997-02-19 | ロレアル | Oxidation dye composition for keratin fibers comprising 2- (β-hydroxyethyl) -para-phenylenediamine, 2-methylresorcinol and 3-aminophenol, and a dyeing method using the same |
| JPH07330558A (en) * | 1994-06-06 | 1995-12-19 | L'oreal Sa | Oxidative dye composition for keratin fiber made of 2-(beta-hydroxyethyl)-para-phenylene diamine,2-methyl resorcinol, and 3-aminophenol and dyeing method using it |
| US5599353A (en) * | 1994-06-06 | 1997-02-04 | L'oreal | Composition for the oxidation dyeing of keratinous fibers comprising 2-(β-hydroxyethyl)-para-phenylenediamine, 2-methylresorcinol and 3-aminophenol, and dyeing process using such a composition |
| US5964898A (en) * | 1994-06-21 | 1999-10-12 | L'oreal | Composition for the oxidation dyeing of keratinous fibers comprising 2-(β-hydroxyethyl)-para-phenylenediamine, 2-methylresorcinol and resorcinol, and dyeing process using such a composition |
| EP0688558A2 (en) * | 1994-06-21 | 1995-12-27 | L'oreal | Composition for dyeing keratinous fibres comprising 2-(beta-hydroxyethyl)-paraphenylene-diamine, 2-methylresorcin and resorcin |
| EP0776652A1 (en) | 1995-11-30 | 1997-06-04 | GOLDWELL GmbH | Oxidation hair dyes containing at least one plant extract |
| EP0857478A2 (en) * | 1997-02-08 | 1998-08-12 | GOLDWELL GmbH | Oxidative hair dye |
| EP0857479A2 (en) * | 1997-02-08 | 1998-08-12 | GOLDWELL GmbH | Oxidative hair dye |
Also Published As
| Publication number | Publication date |
|---|---|
| BE1002856A4 (en) | 1991-07-02 |
| FR2647341A1 (en) | 1990-11-30 |
| EP0400330A1 (en) | 1990-12-05 |
| GB2239265A (en) | 1991-06-26 |
| DE3917304A1 (en) | 1990-11-29 |
| WO1990014818A1 (en) | 1990-12-13 |
| RU2060728C1 (en) | 1996-05-27 |
| DE59000997D1 (en) | 1993-04-15 |
| GB2239265B (en) | 1992-07-29 |
| EP0400330B2 (en) | 2001-03-07 |
| ATA900790A (en) | 1996-04-15 |
| AT402787B (en) | 1997-08-25 |
| ES2055214T3 (en) | 1994-08-16 |
| ES2055214T5 (en) | 2001-08-01 |
| GB9028046D0 (en) | 1991-02-27 |
| FR2647341B1 (en) | 1994-09-23 |
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